Metal-mediated cross-coupling with ring-metalated porphyrins

ABSTRACT

Porphyrins substituted with, for example, vinyl and acetylene groups are provided, along with polymers containing the same. In preferred embodiments, the substituted porphyrins are prepared by coupling halogenated porphyrins with anionic groups via metal-mediated cross-coupling reactions under stoichiometric or catalytic conditions.

RELATED APPLICATION

This is a division of application Ser. No. 08/064,468, filed May 20,1993 issued as U.S. Pat. No. 5,493,017, which is a continuation-in-partof U.S. application Ser. No. 07/929,943 filed Aug. 14, 1992 and issuedas U.S. Pat. No. 5,371,199. The disclosures of which are hereinincorporated by reference.

FIELD OF THE INVENTION

This invention relates to substituted porphyrins and to techniques andintermediates useful in preparing substituted porphyrins. The inventionalso relates to polymers and macromolecules prepared from theporphyrins, and to new and improved uses for the porphyrins and theirpolymers.

BACKGROUND OF THE INVENTION

Porphyrins are derivatives of porphine, a conjugated cyclic structure offour pyrrole rings linked through their 2- and 5-positions by methinebridges. Porphyrins can be covalently attached to other molecules. Theelectronic features of the porphyrin ring system can be altered by theattachment of one or more substituents. The term "porphyrin" includesderivatives wherein a metal atom is inserted into the ring system, aswell as molecular systems in which ligands are attached to the metal.The substituents, as well as the overall porphyrin structure, can beneutral, positively charged, or negatively charged.

Numerous porphyrins have been isolated from natural sources. Notableporphyrin-containing natural products include hemoglobin, thechlorophylls, and vitamin B₁₂. Also, many porphyrins have beensynthesized in the laboratory, typically through condensation ofsuitably substituted pyrroles and aldehydes. However, reactions of thistype generally proceed in low yield, and cannot be used to produce manytypes of substituted porphyrins.

Accordingly, there exists a need in the art for synthetic methodscapable of producing a greater variety of porphyrins than presentlyavailable.

OBJECTS OF THE INVENTION

It is one object of the present invention to provide improved methodsfor synthesizing substituted porphyrins.

It is another object of the invention to provide novel substitutedporphyrins.

It is yet another object to provide novel porphyrin-containingcompounds.

It is a further object of the invention to provide polymers containinglinked porphyrin units.

It is still another object to provide new applications for substitutedporphyrins and porphyrin-containing compounds.

SUMMARY OF THE INVENTION

These and other objects are satisfied by the present invention, whichprovides porphyrins having formula (1), (2), or (3): ##STR1## wherein Mand M' are metal atoms and R_(A1) -R_(A4) and R_(B1) -R_(B8) are,independently, H or chemical functional groups that can bear a negativecharge prior to attachment to a porphyrin compound. In certain preferredembodiments, at least one of R_(A1) -R_(A4) has formula CH═CH₂ or atleast one of R_(A1) -R_(A4) or R_(B1) -R_(B8) has formulaC(R_(C))═C(R_(D))(R_(E)), provided that at least one of R_(C), R_(D),and R_(E) is not H, where R_(C), R_(D), and R_(E) are, independently, H,F, Cl, Br, I, alkyl or heteroalkyl having from 1 to about 20 carbonatoms, aryl or heteroaryl having about 4 to about 20 carbon atoms,alkenyl or heteroalkenyl having from 1 to about 20 carbon atoms, alkynylor heteroalkynyl having from 1 to about 20 carbon atoms, trialkylsilylor porphyrinato; M is a transition metal, a lanthanide, actinide, rareearth or alkaline metal. R_(C), R_(D), and R_(E) also can includepeptides, nucleosides, and/or saccharides.

In other preferred embodiments, at least one of R_(A1) -R_(A4) or R_(B1)-R_(B8) has formula C.tbd.C(R_(D)). In further preferred embodiments, atleast one of R_(A1) -R_(A4) is haloalkyl having from 1 to about 20carbon atoms. In further preferred embodiments, at least one of R_(B1)-R_(B8) is haloalkyl having 2 to about 20 carbon atoms or at least fiveof R_(B1) -R_(B8) are haloalkyl having from 1 to about 20 carbon atomsor haloaryl having from about 4 to about 20 carbon atoms. In furtherpreferred embodiments, at least one of R_(B1) -R_(B8) is haloaryl orhaloheteroaryl having about 4 to about 20 carbon atoms. In still furtherpreferred embodiments, at least one of R_(A1) -R_(A4) or R_(B1) -R_(B8)includes an amino acid, peptide, nucleoside, or saccharide.

The present invention also provides processes and intermediates forpreparing substituted porphyrins. In certain embodiments, the processescomprise providing a porphyrin compound having formula (1), (2), or (3)wherein at least one of R_(A1) -R_(A4) or R_(B1) -R_(B8) is a halogenand contacting the porphyrin compound with a complex having formulaY(L)₂ wherein Y is a metal and L is a ligand. This produces a firstreaction product, which is contacted with an organometallic compoundhaving general formula T(R_(L))_(z) (R_(O)), T(R_(L))_(z) (R_(O))_(y)(X_(B))_(w), T(R_(O))(X_(B)) or T(R_(O))_(y) where T is a metal; X_(B)is a halogen; R_(L) is cyclopentadienyl or aryl having about 6 to about20 carbon atoms; R_(O) is alkyl having 1 to about 10 carbon atoms,alkenyl or alkynyl having 2 to about 10 carbon atoms, aryl having about6 to about 20 carbon atoms; z and w are greater than or equal to 0; andy is at least 1. This contacting produces a second reaction productwhich, through reductive elimination, yields a third reaction productthat contains a porphyrin substituted with R_(O).

In further embodiments, the processes comprise providing a porphyrincompound having formula (1), (2), or (3) wherein at least one of R_(A1)-R_(A4) or R_(B1) -R_(B8) is a halogen and contacting the porphyrincompound with an activated metal Z. This produces a ring-metalatedporphyrin wherein metal Z has inserted into the porphyrin/halogencovalent bond. Alternatively, ring metalation of the halogenatedporphyrin can be carried out with a catalytic amount of Y(L)₂ and analkyltin reagent having formula (R)₃ Sn--Sn(R)₃, where R is alkyl having1 to about 10 carbon atoms, to yield trialkyltin-substituted porphyrin.Either metalated porphyrin can be contacted with a compound havingformula R_(P) -R_(Z), where R_(P) is cyclopentadienyl or aryl havingabout 6 to about 20 carbon atoms, alkyl having 1 to about 10 carbonatoms, alkenyl having 2 to about 10 carbon atoms, or porphyrinato andR_(Z) is a leaving group such as a halogen, a tosylate, or a triflate.Such contacting should be performed in the presence of a catalyst havingformula Y(L)₂, as defined above. This produces a porphyrin substitutedwith R_(P). Alternatively, the first reaction product can be contactedwith an organic or organometallic quenching reagent.

In another aspect, the invention provides polymers comprising linkedporphyrin units. In certain embodiments, porphyrin units having formula(1), (2), or (3) share covalent bonds. In other embodiments, at leastone of R_(A1) -R_(A4) or R_(B1) -R_(B8) function as linking groups. Inthese embodiments, at least a portion of a linking group can haveformula C(R_(C))═C(R_(D)) (R_(E))!_(x), C.tbd.C(R_(D))!_(x), CH₂(R_(C))--CH(R_(D)) (R_(E))!_(x) or CH═CH(R_(D))!_(x) where x is atleast 1. The remaining of R_(A1) -R_(A4) and R_(B1) -R_(B8) can be H,halogen, alkyl or heteroalkyl having 1 to about 20 carbon atoms or arylor heteroaryl having 4 to about 20 carbon atoms, C(RC)═C(R_(D)) (R_(E)),C.tbd.C(R_(D)), or a chemical functional group that includes a peptide,nucleoside, and/or saccharide. In other preferred embodiments, thelinking group is cycloalkyl or aryl having about 6 to about 22 carbonatoms.

The invention also provides processes for preparing porphyrin-containingpolymers. In certain embodiments, the processes comprise providing atleast two compounds that, independently, have formula (1), (2), or (3)wherein at least one of R_(A1) -R_(A4) or R_(B1) -R_(B8) in each of thecompounds contains an olefinic carbon-carbon double bond or a chemicalfunctional group reactive therewith. In other embodiments, at least oneof R_(A1) -R_(A4) or R_(B1) -R_(B8) in each of the compounds contains acarbon-carbon triple bond or a chemical functional group reactivetherewith. The compounds are then contacted for a time and underreaction conditions effective to form covalent bonds through thecarbon-carbon double and/or triple bonds.

The porphyrins and porphyrin-containing polymers of the invention can beused, for example, as dyes, catalysts, contrast agents, antitumoragents, antiviral agents, and in chemical sensors and electroopticaldevices.

BRIEF DESCRIPTION OF THE FIGURES

The numerous objects and advantages of the present invention may bebetter understood by those skilled in the art by reference to theaccompanying figures, in which:

FIG. 1 shows a linear polymer of the invention wherein R_(F1) is acovalent bond or a divalent functional group.

FIG. 2 shows a linear polymer of the invention having diacetyleniclinking groups.

FIG. 3 shows a linear polymer of the invention having monoacetylenic andphenoxy linking groups, wherein R' is alkyl having from 1 to about 20carbon atoms.

FIG. 4 shows a cross-linked polymer of the invention, wherein n, m, v,x, and y are at least 1.

DETAILED DESCRIPTION OF THE INVENTION

It has been found in accordance with the present invention that a widevariety of novel porphyrins can be prepared through metal-mediated crosscoupling of a halogenated porphyrin core and a suitable organometallicmoiety. In general, the resulting porphyrins have formula (1), (2), or(3): ##STR2## wherein M and M' are metal atoms and R_(A1) -R_(A4) andR_(B1) -R_(B8) are, independently, H or a variety of chemical functionalgroups that can bear a negative charge prior to attachment to aporphyrin compound. M preferably is a lanthanide or actinide or a metalsuch as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd,Ag, La, Hf, Ta, W, Re, Os, Ir, Pt, Cd, Hg, Li or Au. More preferably, Mis a metal having a full valence shell, even more preferably Zn or Mg.M' can be a metal such as Li, Na, K, Rb, or Cs, preferably Li.

R_(A1) -R_(A4) and R_(B1) -R_(B8) can be virtually any chemicalfunctional group or covalent assemblage of functional groups which,prior to attachment to a porphyrin compound, can bear a negative charge.In certain embodiments wherein R_(A1) -R_(A4) and R_(B1) -R_(B8) areappended to a porphyrin compound using the methods of the invention,these groups should be capable of bearing a carbon-centered negativecharge (i.e., exist as a carbocentric anion in solution or otherwise).Preferably, R_(A1) -R_(A4) and R_(B1) -R_(B8) are primary or secondaryalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, aryl or heteroaryl.R_(A1) -R_(A4) and R_(B1) -R_(B8) should contain functionality that canwithstand the reaction conditions associated with metal-mediated crosscoupling. Those skilled in the art will recognize that chemicalprotecting groups can be attached to any sensitive functionality foundwithin R_(A1) -R_(A4) and R_(B1) -R_(B8) and then removed after thecoupling reactions have been completed.

Compounds having formulas (1)-(3) preferably bear 1, 2, 4, 8, or 12substituents (i.e., 1, 2, 4, 8, or 12 of R_(A1) -R_(A4) and R_(B1)-R_(B8) are not H). More preferably, these compounds bear 2 or 4substituents that contain alkenyl or alkynyl functionality.

In certain embodiments, at least one of R_(A1) -R_(A4) has formulaCH═CH₂. In other embodiments, at least one of R_(A1) -R_(A4) or R_(B1)-R_(B8) has formula C(R_(C))═C(R_(D)) (R_(E)), provided that at leastone of R_(C), R_(D), and R_(E) is not H, or at least one of R_(A1)-R_(A4) or R_(B1) -R_(B8) has formula C.tbd.C(R_(D)). In furtherpreferred embodiments, at least one of R_(A1) -R_(A4) is haloalkylhaving from 1 to about 20 carbon atoms. In further preferredembodiments, at least one of R_(B1) -R_(B8) is haloalkyl having 2 toabout 20 carbon atoms or at least five of R_(B1) -R_(B8) are haloalkylhaving from 1 to about 20 carbon atoms. In further preferredembodiments, at least one of R_(B1) -B_(B8) is haloaryl orhaloheteroaryl having about 4 to about 20 carbon atoms. Preferredhalogenated moieties are fully halogenated (e.g., CF₃). In still furtherembodiments, at least one of R_(A1) -R_(A4) or R_(B1) -R_(B8) is asingle amino acid or a terminal amino acid of a polypeptide.

R_(C), R_(D), and R_(E) can be any of a wide variety of chemicalfunctional groups. Preferably, R_(C), R_(D), and R_(E) are,independently, H, F, Cl, Br, I, alkyl or heteroalkyl having from 1 toabout 20 carbon atoms, aryl or heteroaryl having about 4 to about 20carbon atoms, alkenyl or heteroalkenyl having from 2 to about 20 carbonatoms, alkynyl or heteroalkynyl having from 2 to about 20 carbon atoms,trialkylsilyl, or porphyrinato. The terms heteroalklyl and heteroarylare intended to denote moieties wherein a heteroatoms is inserted intothe carbon backbone of an alkyl or aryl structure (e.g., ether,thioether, and pyridinyl groups). Representative heteroatoms include N,O, S, Se, and Te. The terms alkyl, aryl, alkenyl, and alkynyl areintended to include moieties substituted with, for example, halogens ornitro, acid, alkyl, or ester groups. Preferred alkyl and aryl groupshave from 1 to about 10 carbon atoms and about 6 to about 14 carbonatoms, respectively. Preferred alkenyl and alkynyl groups have from 2 toabout 10 carbon atoms. R_(C), R_(D), and R_(E) preferably are alkyl,aryl, or trialkylsilyl.

R_(C), R_(D), and/or R_(E) also can be chemical functional groups thatinclude at least one peptide, nucleoside, and/or saccharide. Forexample, R_(C), R_(D), and R_(E) can include a polymethylene chainconnecting a DNA- or RNA-cleaving compound having formula (1), (2), or,in the absence of water, (3) with an oligonucleotide. (see, e.g., Stein,et al., Cancer Research 1988; 48, 2659). As will be recognized, peptidesare compounds comprising two or more amino acids covalently boundthrough an amide linkage (e.g., glycylalanine), nucleosides areglycosides comprising covalently bound pentoses and heterocyclic bases(e.g., cytidine), and saccharides are hemiacetal forms of polyhydroxyaldehydes and ketones (e.g., sucrose). Each of these terms is intendedto include both naturally occurring and non-naturally occurringmoieties.

In preferred embodiments, each of R_(A1) -R_(A4) is alkyl or aryl andeither R_(B5), R_(B5) and R_(B1), or R_(B5) and R_(B2) have formulaC.tbd.C(R_(D)).In other preferred embodiments, each of R_(A1) -R_(A4) isalkyl or aryl and each of R_(B1) -R_(B8) have formula C.tbd.C(R_(D)). Instill other preferred embodiments, R_(A1) has formula C.tbd.C(R_(D)),each of R_(A2) -R_(A4) are alkyl or aryl, at least one of R_(B1) -R_(B8)is H, alkyl or aryl, and R_(D) is H, F, Cl, Br, I, alkyl, aryl, alkenyl,alkynyl, trialkylsilyl, or porphyrinato. In other preferred embodiments,R_(A1) and R_(A3) have formula C.tbd.C (R_(D)), R_(A2) and R_(A4) arealkyl, aryl or a halogen, at least one of R_(B1) -R_(B8) is H, alkyl,aryl or a halogen, and R_(D) is H, F, Cl, Br, I, alkyl, aryl, alkenyl,alkynyl, trialkylsilyl, or porphyrinato; more preferably R_(D) is3,4,5-trialkyl-substituted phenyl or 3,4,5-trialkyloxy-substitutedphenyl with the alkyl and alkoxy substituents having about 7 to about 20carbon atoms. In still other preferred embodiments, R_(A1) -R_(A4) haveformula C.tbd.C (R_(D)), at least one of R_(B1) -R_(B8) is H, alkyl,aryl or a halogen, and R_(D) is H, F, Cl, Br, I, alkyl, aryl, alkenyl,alkynyl, trialkylsilyl, or porphyrinato, more preferably R_(D) is H,3,4,5-trialkyl-substituted phenyl, or 3,4,5-trialkoxy-substituted phenylwith the alkyl and alkoxy substituents having about 7 to about 20 carbonatoms.

In certain embodiments, the porphyrins of the invention are prepared bymetal-mediated cross coupling of a halogenated, preferably brominated,chlorinated, or iodinated, porphyrin with an organometallic moiety. Inother embodiments, the porphyrins of the invention are prepared bymetal-mediated cross coupling of a metalated porphyrin with an organicmoiety bearing a suitable leaving group. As will be recognized, thelatter methods provide a means for attaching chiral substituents to aporphyrin core. Both metalated porphyrins (e.g., formulas (2) and (3))and non-metalated porphyrins (e.g., formula (1)) can be used in theprocesses of the invention; the cross-coupling products can be metalatedand de-metalated, as desired. The principles and techniques relating tometal-mediated cross coupling are well known to those skilled in the artto consist of three general steps: (1) oxidative addition, (2)transmetalation, and (3) reductive elimination. (See, e.g., Collman, etal., Principles and Applications of Organotransition Metal Chemistry,University Science Books, 1987, Mill Valley, Calif.; Kumada, Pure &Appl. Chem., 1980, 52, 669; Hayashi, et al., Tetrahedron Letters, 1979,21, 1871.)

In accordance with certain embodiments of the invention, a halogenatedporphyrin, P_(N) -X_(A), is contacted with a catalyst having formulaY(L)₂ where Y is a metal such as, for example, Pd, Ni, Pt, Ru, or Cu andL is a ligand appropriate for that metal. When Y is Pd or Ni, L shouldbe a phosphorous-, nitrogen-, arsenic-, or antimony-containing Lewisbase such as an alkyl- or arylphosphine, an alkyl or arylarsenine, analkyl- or arylstibene, a nitrogen-containing heterocycle such aspyridine, or a mixture thereof. The terms alkylphosphine, arylphosphine,alkylarsenine, arylarsenine, alkylstibene, and arylstibene are intendedto describe moieties having at least one alkyl or aryl substituent suchas, for example, monoalkylphosphines, trialkylphosphines, anddialkylmonoarylphosphines. Contacting the halogenated porphyrin with thecatalyst complex is believed to produce a second compound having formulaP_(N) --Y(L)₂ X_(A), which is contacted with an organometallic compoundhaving formula T(R_(L))_(z) (R_(O)), T(R_(L))_(z) (R_(O))_(t)(X_(B))_(w), T(R_(O)) (X_(B)) or T(R_(O))_(t) where T is a metal suchas, for example, Li, Na, K, Rb, Cs, Hg, Sn, Al, B, Si, Zn, Zr, Cd, Cu,or Mg; X_(B) is a halogen or an alkoxy group; R_(L) is cyclopentadienylor aryl having about 6 to about 20 carbon atoms; R_(O) is alkyl, alkenylor alkynyl having 1 to about 10 carbon atoms, aryl having about 6 toabout 20 carbon atoms such as C(R_(C))═C(R_(D))(R_(E)), C.tbd.C(R_(D)),haloalkyl groups or haloaryl groups; z and w are greater than or equalto 0; and t is at least 1. T can be any metal that does not participatein an outer sphere electron transfer reaction with the porphyrin.Representative organometallic compounds are CuR_(O), Zn(R_(O))₂, ZnR_(O)X_(B), (nBu)₃ SnR_(O), and Cp₂ ZrR_(O) X_(B) (Cp=cyclopentadienyl). Thiscontacting is believed to produce a third compound having formula P_(N)-Y(L)₂ R_(O) which, through reductive elimination, is transformed intosubstituted porphyrin P_(N) -R_(O).

In other embodiments of the invention, metalated porphyrins are preparedby contacting halogenated porphyrins, P_(N) -X_(A), with an activatedmetal Z. Alternatively, ring metalation of the halogenated porphyrin canbe carried out with a catalytic amount of Y(L)₂ and an alkyltin reagenthaving formula (R)₃ Sn--Sn(R)₃, where R is alkyl having 1 to about 10carbon atoms, to yield trialkyltin-substituted porphyrin. Z can be anymetal that does not participate in an outer sphere electron transferreaction with the porphyrin. Z preferably is Zn, Mg, Ca, Cd, Cu, Sn, Sr,Ba, or Zr. Preferably, the activated metal is prepared by contacting ametal reagent having formula Z(X_(C))_(c) where Z is a metal, X_(C) is ahalogen, and c is 1-4, with a reducing agent under conditions effectiveto reduce the metal reagent. In embodiments wherein the metal reagent isreduced in the presence of the porphyrin compound, the reducing agentshould be effective to reduce the metal reagent but ineffective toreduce the porphyrin compound. Activated metals according to theinvention can be prepared by, for example, the method of Ebert andRieke, J. Org. Chem. 1984, 49, 5280 and J. Org. Chem. 1988, 53, 4482.

The metalated porphyrins can be contacted with compounds having formulaR_(P) -R_(Z), where R_(P) is cyclopentadienyl or aryl having about 6 toabout 20 carbon atoms, alkyl having 1 to about 10 carbon atoms, alkenylhaving 2 to about 10 carbon atoms, or porphyrinato and R_(Z) is aleaving group. Leaving groups include but are not limited halogen,alkylsulfonyl, substitutedalkylsulfonyl, arylsulfonyl, substitutedarylsulfonyl, hetercyclcosulfonyl or trichloroacetimidate. Preferredleaving groups include chloro, fluoro, bromo, iodo,p-(2,4-dinitroanilino)benzenesulfonyl, benzenesulfonyl, methylsulfonyl(mesylate), p-methylbenzenesulfonyl (tosylate), p-bromobenzenesulfonyl,trifluoromethylsulfonyl (triflate), trichloroacetimidate, acyloxy,2,2,2-trifluoroethanesulfonyl, imidazolesulfonyl, and2,4,6-trichlorophenyl. Contacting should be performed in the presence ofa catalyst having formula Y(L)₂ where Y is a metal such as, for example,Pd, Ni, Pt, Ru, or Cu and L is a ligand appropriate for that metal. WhenY is Pd or Ni, L should be a phosphorous-, nitrogen-, arsenic-, orantimony-containing Lewis base such as an alkyl- or arylphosphine, analkyl or arylarsenine, an alkyl- or arylstibene, a nitrogen-containingheterocycle such as pyridine, or a mixture thereof.

Ring-metalated porphyrins alternatively can be contacted with organic ororganometallic quenching reagents. Representative organic quenchingreagents include those commonly used in the well known Grignardreaction, such as, for example, CO₂, esters, aldehydes, ketones, acidchlorides, and amides. (see, e.g., J. March, Advanced Organic Chemistry,John Wiley & Sons, 1985, New York) Organometallic quenching reagentsinclude those disclosed by Azizian, et al., J. Organomet. Chem. 1981,215, 49 and Barbero, et al., J. Chem. Soc. Chem. Commun. 1992, 351, suchas, for example, trialkyl tin halides and trialkyl borates.

In general, the coupling reactions of the present invention proceedrapidly and in excellent yield, contrary to teaching in the prior artthat reactions of this type should not work well with electron-richsystems such as porphyrins. It has been found that not all of the metalsknown for use in metal-mediated cross coupling reactions can be used toprepare substituted porphyrins. For example, coupling reactions whereinthe metal T is lithium or magnesium have been found to proceed, if atall, in very low yield and with destruction of the porphyrin startingmaterial. Also, coupling reactions wherein the metal Z is lithium,potassium, or sodium preferably are avoided.

The use of metal-mediated cross coupling in accordance with theinvention can produce monomeric compounds suitable for incorporationinto porphyrin-containing homopolymers or copolymers or intomacromolecular or supramolecular species containing, for example, one ormore peptides, nucleosides, or saccharides. Alternatively,metal-mediated cross-coupling can be used to directly prepareporphyrin-containing homopolymers or copolymers. The polymers accordingto the invention can contain as few as 2 porphyrin units, but morepreferably contain at least 3 porphyrin units, more preferably at least5 porphyrin units. In certain embodiments, polymers of the inventioncomprise a plurality of porphyrin units that, independently, haveformula (1), (2), or (3) wherein at least one of R_(B1) -R_(B8) orR_(A1) -R_(A4) includes a linking group selected fromC(R_(C))═C(R_(D))(R_(E))!_(x), C.tbd.C (R_(D))!_(x), CH₂(R_(C))-CH(R_(D)) (R_(E))!_(x) or CH═CH(R_(D))!_(x) where x is atleast 1. Preferably, the remaining of R_(A1) -R_(A4) are, independently,H, alkyl, alkenyl, alkynyl, or aryl and the remaining of R_(B1) -R_(B8)are, independently, H, alkyl, aryl, C(R_(C))═C(R_(D))(R_(E)), or C.tbd.C(R_(D)).

In other embodiments, polymers according to the invention comprise aplurality of porphyrin units that, independently, have formula (1), (2),or (3) wherein at least one of R_(B1) -R_(B8) or R_(A1) -R_(A4) is acycloalkyl, cycloalkenyl, aryl or heteroaryl linking group having about6 to about 22 carbon atoms.

Those skilled in the art will recognize the wide variety of polymersthat can be prepared from the porphyrin-containing compounds of theinvention. In certain embodiments, cofacial polymers are formed having,for example, formula (4). (see, e.g., Durand, et al., J. Am. Chem. Soc.,1983, 105, 2710). ##STR3##

In other embodiments, somewhat linear polymer chains are formed whereina portion of the polymer has general formula (P_(N))_(r) where P_(N) isa porphyrin unit and r is at least 2. In further embodiments, linearpolymer chains have general formula:

     --(Q.sub.L).sub.l --(P.sub.N).sub.s --!.sub.h

where Q_(L) is a linking group, P_(N) is a porphyrin unit, and h, l, ands are independently selected to be at least 1. For example, a portion ofsuch polymers can have formula:

     --(P.sub.N1).sub.s' --(Q.sub.L1).sub.l' --(P.sub.N2).sub.s" --(Q.sub.L2).sub.l" --!.sub.l

wherein P_(N1) and P_(N2) are independently selected porphyrin units,Q_(L1) and Q_(L2) are independently selected linking groups, and l', l",s', and s" are at least 1. These essentially linear polymer chains canbe cross-linked such that a portion of the polymer has general formula:

     --(Q.sub.H).sub.h --(P.sub.N).sub.u --!.sub.v

wherein Q_(H) is a linking group, and h, u, and v are independentlyselected to be at least 1. A portion of these cross-linked polymers canhave formula:

     --(P.sub.N3).sub.u' --(Q.sub.H1).sub.h' --(P.sub.N1).sub.u" --(Q.sub.H2).sub.h' --!.sub.v

wherein P_(N3) is a porphyrin unit, Q_(H1) and Q_(H2) are independentlyselected linking groups, and h', h", u', and u" are at least 1. Thus,cross-linked polymers can have formulas: ##STR4## where r' is at least1.

The polymers of the invention can be formed by contacting a substitutedporphyrin with a second compound containing functionality that isreactive with the functionality contained within the porphyrin.Preferably, the porphyrin contains an olefinic carbon-carbon doublebond, a carbon-carbon triple bond or some other reactive functionality.The contacting should be performed under conditions effective to form acovalent bond between the respective reactive functionalities.Preferably, porphyrin-containing polymers are formed by metal-mediatedcross-coupling of, for example, dibrominated porphyrin units. Also,porphyrin-containing polymers can be synthesized using known terminalalkyne coupling chemistry. (see, e.g., Patai, et al., The Chemistry ofFunctional Groups, Supplement C, Part 1, pp. 529-534, Wiley, 1983;Cadiot, et al., Acetylenes, pp. 597-647, Marcel Dekker, 1964; andEglinton, et al., Adv. Org. Chem., 1963, 4, 225). As will be recognized,the second compound noted above can be a substituted porphyrin of theinvention or some other moiety such as an acrylate monomer. Thus, a widevariety of copolymeric structures can be synthesized with the porphyrinsof the invention. Through careful substituent selection the porphyrinsof the invention can be incorporated into virtually any polymeric matrixknown in the art, including but not limited to polyacetylenes,polyacrylates, polyolefins, polyethers, polyurethanes, polycarbonates,polyanilines, polypyrroles, and polythiophenes. For example, fluorescentporphyrins can be incorporated into such polymers as end-capping groups.

The porphyrins and porphyrin-containing polymers of the invention can beused, for example, as dyes, catalysts, contrast agents, antitumoragents, antiviral agents, liquid crystals, in chemical sensors and inelectrooptical and solar energy conversion devices. They also can beincorporated into supramolecular structures. The polymers andsupramolecular structures, which anchor porphyrin units in a relativelystable geometry, should improve many of the known uses for porphyrinsand even provide a number of new uses, such as in a solid phase systemfor sterilizing virus-containing solutions. Representative uses aredisclosed by, for example, the following patents, which are incorporatedherein by reference: U.S. Pat. No. 4,895,682 (Ellis, et al.); U.S. Pat.No. 4,986,256 (Cohen); U.S. Pat. No. 4,668,670 (Rideout, et al.); U.S.Pat. No. 3,897,255 (Erickson); U.S. Pat. No. 3,899,334 (Erickson); U.S.Pat. No. 3,687,863 (Wacher); U.S. Pat. No. 4,647,478 (Formanek, et al.);and U.S. Pat. No. 4,957,615 (Ushizawa, et al.). Further uses aredisclosed are disclosed by, for example, U.K. Patent Application2,225,963 (Casson, et al.); International Application WO 89/11277(Dixon, et al.); International Application WO 91/09631 (Matthews, etal.); European Patent Application 85105490.8 (Weishaupt, et al.);European Patent Application 90202953.7 (Terrell, et al.); EuropeanPatent Application 89304234.1 (Matsushima, et al.) ; Lehn, Angew. Chem.Int. Ed. Engl., 1988, 27, 89; Wasielewski, Chem. Rev., 1992, 92, 435;Mansury, et al., J. Chem. Soc., Chem. Comm., 1985, 155; Groves, et al.,J. Am. Chem. Soc., 1983, 105, 5791; and Giroud-Godquin, et al., Angew.Chem. Int. Ed. Engl., 1991, 30, 375. It is believed that the porphyrinsof the invention can be substituted for the porphyrins disclosed in eachof the foregoing publications.

Additional objects, advantages, and novel features of this inventionwill become apparent to those skilled in the art upon examination of thefollowing examples thereof, which are not intended to be limiting.

EXAMPLE 1 5,15-DIPHENYLPORPHYRIN

A flame-dried 1000 ml flask equipped with a magnetic stirring bar wascharged with 2,2-dipyrrylmethane (458 mg, 3.1 mmol), benzaldehyde (315μl, 3.1 mmol), and 600 ml of freshly distilled (CaH₂) methylenechloride. The solution was degassed with a stream of dry nitrogen for 10minutes. Trifluoroacetic acid (150 μl, 1.95 mmol) was added via syringe,the flask was shielded from light with aluminum foil, and the solutionwas stirred for two hours at room temperature. The reaction was quenchedby the addition of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 900mg, 3.96 mmol) and the reaction was stirred for an additional 30minutes. The reaction mixture was neutralized with 3 ml of triethylamineand poured directly onto a silica gel column (20×2 cm) packed in hexane.The product was eluted in 700 ml of solvent. The solvent was evaporated,leaving purple crystals (518 mg., 1.12 mmol, 72.2%). This product wassufficiently pure for further reactions. Vis(CHCl₃): 421 (5.55), 489(3.63), 521 (4.20), 556 (4.04), 601 (3.71), 658 (3.73).

EXAMPLE 2 5,15-DIBROMO-10,20-DIPHENYLPORPHYRIN

5,15-Diphenylporphyrin (518 mg, 1.12 mmol) was dissolved in 250 ml ofchloroform and cooled to 0° C. Pyridine (0.5 ml) was added to act as anacid scavenger. N-Bromosuccinimide (400 mg, 2.2 mmol) was added directlyto the flask and the mixture was followed by thin-layer chromatography(TLC; 50% CH₂ Cl₂ /hexanes eluant). After 10 minutes the reactionreached completion and was quenched with 20 ml of acetone. The solventswere evaporated and the product was washed with several portions ofmethanol and pumped dry to yield 587 mg (0.94 mmol, 85%) ofreddish-purple solid. The compound was sufficiently pure to use in thenext reaction. Vis(CHCl₃): 421 (5.55), 489 (3.63), 521 (4.20), 556(4.04), 601 (3.71), 658 (3.73).

EXAMPLE 3 5,15-DIBROMO-10,20-DIPHENYLPORPHYRINATO ZINC

5,15-Dibromo-10,20-diphenylporphyrin (587 mg, 0.94 mmol) was suspendedin 30 ml DMF containing 500 mg ZnCl₂. The mixture was heated at refluxfor 2 hours and poured into distilled water. The precipitated purplesolid was filtered through a fine fritted disk and washed with water,methanol, and acetone and dried in vacuo to yield 610 mg (0.89 mmol,95%) of reddish purple solid. The compound was recrystallized fromtetrahydrofuran (THF)/heptane to yield large purple crystals of thetitle compound (564 mg, 0.82 mmol, 88%). Vis(THF): 428 (5.50), 526(3.53), 541 (3.66), 564 (4.17), 606 (3.95).

EXAMPLE 4 MESO-SUBSTITUTED PORPHYRINS

General Procedure

In each of the following examples,5,15-Dibromo-10,20-diphenylporphyrinato zinc (0.1 mmol), and Pd(PPh₃)₄(0.0025 mmol) were dissolved in 35 ml of distilled, degassed THF in asealed storage tube with the 1 mmol of the indicated organometallicreagent and warmed at 60° C. for 48 hours. The reaction was monitored byTLC on withdrawn aliquots. The mixture was quenched with water,extracted with chloroform, dried over CaCl₂, evaporated and purified bycolumn chromatography.

A. 5,15-Diphenyl-10,20-dimethylporphyrinato zinc

The organometallic reagent was methyl zinc chloride prepared from methyllithium and anhydrous zinc chloride in THF.

The crude solid was dissolved in THF/heptane, poured onto 10 g silicagel and evaporated to dryness. This silica gel was loaded onto a columnpacked in 50% CH₂ Cl₂ /hexane. A single band was eluted (50% CH₂ Cl₂/hexane) to yield pure 5,15-diphenyl-10,20-dimethylporphyrinato zinc (48mg, 88%). An analytical sample was recrystallized from THF/heptane byslow evaporation under N₂. ¹ H NMR (500 MHz, 3:1 CDCl₃, D₈ -THF) δ 9.34(d, 4H, J=4.6); 8.71 (d, 4H, J=4.6); 8.02 (dd, 4H, J₁ =7.5, J₂ =1.4);7.57 (m, 6H); 4.51 (s, 6H). ¹³ C NMR (125 MHz, 3:1 CDCl₃, D₈ -THF) δ150.07(0), 148.88(0), 143.34(0), 134.18(1), 131.42(1), 128.09(1),126.73(1), 125.88(1), 119.29(0), 113.74(0), 20.81(3). Vis (THF) 424(5.58), 522 (3.40), 559 (4.12); 605 (3.88).

B. 5,15-Diphenyl-10,20-divinylporphyrinato zinc

The organometallic reagent was tri-n-butylvinyl tin.

The crude product was absorbed on silica and loaded onto a column packedin hexane. Elution was carried out with CH₂ Cl₂ (0-50%)/hexane. A smallquantity of purple material led the main fraction. The main band wasevaporated to yield pure 5,15-diphenyl-10,20-divinylporphyrinato zinc(53 mg, 91%). An analytical sample was recrystallized from chloroform. ¹H NMR (500 MHz, CDCl₃) δ9.52 (d, 4H, J=4.7); 9.24(dd, 2H, J₁ =17.3, J₂=9.1); 8.92 (d, 4H, J=4.7); 8.19 (dd, 4H, J₁ =6.8, J₂ =2.0); 7.75 (m,6H); 6.48 (dd, 2H, J₁ =11.0, J₂ =1.9); 6.05 (dd, 2H, J₁ =17.3, J₂ =2.0).¹³ C NMR (125 MHz, CDCl₃) δ 163.40(1), 149.90(0), 149.21(0), 142.83(0),137.97(0), 134.40(1), 132.10(1), 130.39(1), 127.50(1), 126.73(2),126.57(1), 121.05(0).

C. 5,15-Bis(2,5-dimethoxyphenyl)-10,20-diphenylporphyrinato zinc

The organometallic reagent was 2,5-dimethoxyphenyl lithium, preparedfrom 1,4-dimethoxybenzene and t-butyl lithium in ether at -78° C. Theorganolithium reagent was added to a solution of ZnCl₂ in THF to yieldthe organozinc chloride reagent. This reagent was used immediately.

At the completion of the reaction two highly fluorescent spots werevisible by TLC. The crude product was chromatographed on silica usingCHCl₃ as eluant. The first band off the column proved to be the C_(2h)isomer of 5,15-bis(2,5-dimethoxyphenyl)-10,20-diphenylporphyrinato zinc.This band was evaporated leaving 33 mg (42%) of pure product. Ananalytical sample was recrystallized from chloroform. ¹ H NMR (500MHz,CDCl₃) δ 8.91 (s, 8H); 8.22 (d, 4H, J=6.5); 7.75 (m, 6H); 7.59 (d,2H, J=2.2); 7.26 (broad s, 4H); 3.86 (s, 6H); 3.54 (s, 6H). ¹³ C NMR(125 MHz, CDCl₃) δ 154.10(0), 152.30(0), 150.13(0), 143.00(0),134.10(1), 132.62(0), 132.00(1), 131.44(1), 127.35(1), 126.44(1),121.34(1), 120.69(0), 116.59(0), 114.76(1), 112.31(1), 56.70(3),55.95(3). Vis - 424 (5.64), 551 (4.34), 584 (3.43).

The C_(2v) isomer followed the C_(2h) isomer off the column. The solventwas evaporated leaving 30 mg (32%) of pure5,15-bis(2,5-dimethoxyphenyl)-10,20-diphenylporphyrinato zinc. Thiscompound is much more soluble in chloroform than the C_(2h) isomer. Theassignment of stereochemistry was made from the NMR data. ¹ H NMR (500MHz,CDCl₃) δ 8.90 (s, 8H); 8.21 (d, 2H, J=7.9); 8.19 (d, 2H, J=6.5);7.73(m, 6H); 7.58 (s, 2H); 7.24 (broad s, 4H); 3.84(s, 6H); 3.53 (s, 6H). ¹³C NMR (125 MHz CDCl₃) δ 154.14(0); 152.31(0), 150.15(0), 142.94(0),134.40(1), 132.66(0), 132.02(1), 131.48(1), 127.37(1), 126.46(1),126.44(1), 121.30(1), 120.72(0), 116.69(0), 114.73(1), 112.28(1),56.75(3), 55.92(3).

D. 5,15-Bis(4-methyl)-4'methyl-2,2'-dipyridyl)!-10,20-diphenylporphyrinato zinc

The organometallic reagent was tri-n-butyl(4-methyl)-4'methyl-2,2'-dipyridyl)! tin, prepared by lithiating4,4'-dimethyl-2,2'-dipyridyl with one equivalent of lithiumdiisopropylamide in THF at -78° C. and warming the reaction mixture toroom temperature. The organolithium reagent was treated with 1.1equivalent of tributyltin chloride. The resulting organotin reagent wasused without further purification.

Chromatography of the crude reaction mixture was carried out on silicawith a mixture of CH₂ Cl₂, isopropanol, and triethylamine. The porphyrinwas eluted in one broad band. The product obtained from this procedure(68% yield) was contaminated with a small amount (0.2 eq per eq ofporphyrin) of triphenylphosphine. ¹ H NMR (500 MHz, CDCl₃) δ 9.37 (d,4H, J=4.7); 8.87 (d, 4H, J=4.7); 8.52 (s, 2H); 8.29 (d, 2H, J=5.1); 8.20(d, 2H, J=5.2); 8.10 (m, 6H); 7.71 (m, 6H); 7.01 (d, 2H, J=5.0); 6.88(d, 2H, J=4.2); 6.46 (s, 4H); 2.32 (s, 6H).

E. 5,15-Bis(trimethylsilylethynyl)-10,20-diphenylporphyrinato zinc

The organometallic reagent was trimethylsilyl ethynyl zinc chlorideprepared from trimethylsilylethynyl lithium and anhydrous zinc chloridein THF.

After 48 hours the reaction was bright green. The crude solid wasabsorbed on silica gel, loaded onto a column packed in hexane, andchromatographed with 20%-30% CH₂ Cl₂ /hexane. Clean separation of theproduct from the small quantities of deprotected products were obtainedby this method. The solvents were evaporated and the purple solid waswashed twice with hexane and dried in vacuo. ¹ H NMR (500 MHz, CDCl₃) δ9.68 (d, 4H, J=4.6); 8.89 (d, 4H, J=4.6); 8.15 (dd, 4H, J₁ =7.9, J₂=1.7); 7.75 (m, 6H); 0.58 (s, 18H). ¹³ C NMR (125 MHz, CDCl₃) δ152.22,150.26, 142.10, 134.39, 132.77, 131.29, 127.69, 126,67, 115.08, 107.34,102.00, 0.32.

EXAMPLE 5 PYRROLE-SUBSTITUTED PORPHYRINS

General Procedure

2-Bromo-5,10,15,20-tetraphenylporphyrinato zinc (0.1 mmol) and palladium1,1'-bis(diphenylphosphino)ferrocene) dichloride (Pd(dppf)Cl₂, 7 mg)were combined with 1.0 mmol of the organometallic reagent indicatedbelow in 35 ml dry, degassed THF. The solution was allowed to stand for12 hours, the solvent evaporated, and the compound purified by flashchromatography.

A. 2-Vinyl-5,10,15,20-tetraphenyl porphyrinato zinc

The organometallic reagent was tributylvinyl tin.

The crude reaction mixture was chromatographed on silica and eluted with50% CH₂ Cl₂ /hexane. ¹ H NMR (250 MHz, CDCl₃) δ 8.97 (s, 1H); 8.90 (m,4H); 8.87 (d, 1H, J=4.7); 8.79 (d, 1H, J=4.7); 8.20 (m, 6H); 8.06 (d,2H, J=6.6); 7.74 (m, 12H); 6.39 (dd, 1H, J₁ =17.0, J₂ =9.1); 5.83 (dd,1H, J₁ =17.1, J₂ =2.0); 5.01 (dd, 1H, J₁ =10.7, J₂ =2.0). Vis (CHCl₃)426 (5.53), 517 (3.68); 555 (4.22), 595 (3.68).

B. 2-(2,5-dimethoxyphenyl)-5,10,15,20-tetraphenyl porphyrinato zinc

The organometallic reagent was 2,5-dimethoxyphenyl zinc chloride,prepared from the corresponding lithium reagent and anhydrous zincchloride in THF/diethyl ether.

Flash chromatograph of the crude reaction mixture was carried out withchloroform. The title compound was isolated in 78% yield. ¹ H NMR (500MHz, CDCl₃) δ =8.94 (d, 1H, J=4.7); 8.93 (s,2H); 8.92 (d, 1H, J=4.8);8.85 (s, 1H); 8.84 (d, 1H, J=4.7); 8.70 (d, 1H, J=4.7); 8.23 (m, 6H);7.98 (d, 1H, J=7.0); 7.70 (m, 10H); 7.25 (quintet, 2H, J=7.4); 7.15 (t,1H, J=7.0; 6.92 (d, 2H, J=3.1); 6.54 (dd, 1H, J₁ =9.0, J₂ =3.2); 6.40(d, 1H, J=9.1); 3.68 (s, 3H); 3.42 (s, 3H). ¹³ C NMR (125 MHz, CDCl₃) δ=152.59(0), 151.33(0), 150.46(0), 150.31(0), 150.27(0), 150.15(0),150.12(0), 150.03(0), 148.30(0), 147.16(0), 143.32(0), 142.97(0),142.86, 140.71(0), 135.63(1), 135.20(1), 134.45(1), 134.13(1),132.52(1), 132.02(1), 131.91(1), 131.82(1), 131.32(1), 129.27(0),127.44(1), 127.38(1), 127.18(1), 126.53(1), 126.50(1), 124.91(1),124.70(1), 122.36(0), 121.30(0), 120.91(0), 120.54(0), 118.15(1),113.03(1), 110.35(1), 55.98(3), 54.87(3). Vis (CHCl₃) 421.40 (5.60),513.2 (3.45), 549.75 (4.28), 587.15 (3.45).

C. 2-(Trimethylsilyl ethynyl)-5,10,15,20-tetraphenyl porphyrinato zinc

The organometallic reagent, trimethylsilylacetylide zinc chloride, wasprepared from the corresponding lithium reagent and anhydrous zincchloride in THF.

The crude reaction mixture was chromatographed on silica and eluted with50% CH₂ Cl₂ /hexane. ¹ H NMR (250 MHz, CDCl₃) δ 9.25 (s, 1H); 8.89 (m,4H); 8.85 (d, 1H, J=4.9); 8.76 (d, 1H, J=4.9); 8.16 (m. 6H); 8.09 (d,2H, J=7.1); 7.67 (m, 12H); 0.21 (s, 9H). Vis (CHCl₃) 431 (5.43), 523(shoulder); 559 (4.18), 598 (3.67).

D. 2-n-butyl-5,10,15,20-tetraphenyl porphyrinato zinc

Butylzinc chloride was prepared from n-butyllithium and anhydrous zincchloride in THF.

The crude reaction mixture was chromatographed on silica and eluted with50% CH₂ Cl₂ /hexane. ¹ H NMR (250 MHz, CDCl₃) δ 8.97 (m, 4H); 8.91 (d,1H, J=4.7); 8.77 (d, 1H, J=4.7); 8.74 (s, 1H); 8.22 (m, 6H); 8.13 (d,2H, J=7.3); 7.77 (m, 12H); 2.81 (t, 2H, J=7.7); 1.83 (quint, 2H, J=7.8);1.30 (quint, 2H, J=7.6); 0.91 (t, 3H, J=8.2).

EXAMPLE 6 VINYLIC-BRIDGED PORPHYRINS AND THEIR POLYMERS

A. cis-Bis-1,2- 5-(10,15,20-triphenylporphyrinato)zinc! ethene

5-Bromo-10,15,20-triphenylporphyrinato zinc (0.2 mmol) and Pd(PPh₃)₄(0.02 mmole) are dissolved in 25 ml dry, degassed THF. A solution ofcis-bis(tri-n-butyltin)ethene (0.2 mmol) in 5 ml THF is added and thesolution heated at reflux for 2 days. The reaction is quenched withwater, extracted with methylene chloride, dried over calcium chloride,and the solvents are evaporated. The crude solid is chromatographed onsilica using methylene chloride/hexane eluant to isolate a dimer havingformula (3), wherein R_(A1), R_(A3), and R_(A4) are phenyl and M is Zn.

B. cis-Bis-1,2-{5-10,15,20-tris(pentafluorophenyl)!-2,3,7,8,12,13,17,18-octakis(trifluoromethyl)porphyrinatozinc}-1,2-difluoroethene

5-Bromo-10,15,20-tris(pentafluorophenyl)porphyrinato zinc (0.2 mmol) andPd(PPh₃)₄ (0.02 mmol) are dissolved in 25 ml dry THF. A solution ofcis-bis(tri-n-butyltin)-1,2-difluoroethene (0.2 mmol) in 5 ml THF isadded and the solution heated at reflux for 2 days. The reaction isquenched with water, extracted with methylene chloride, dried overcalcium chloride, and the solvents evaporated. The crude solid ischromatographed on silica using methylene chloride/hexanes eluent toisolate cis-bis-1,2-{5-10,15,20-tris(pentafluorophenyl)porphyrinatozinc}-1,2-difluoroethene.This material is dissolved in chloroform and reacted with a large excessof N-bromosuccinimide as in Example 2 to perbrominate positions R_(B1)-R_(B8) on both porphyrins. The resulting material filtered through afine fritted disk and washed with water, methanol, and acetone, dried invacuo, and then recrystallized from THF/heptane. cis-Bis-1,2-{5-10,15,20-tris(pentafluoro-phenyl)-2,3,7,8,12,13,17,18-octabromoporphyrinato zinc is reacted withPd(dppf) and a large excess of CuCF₃ in the dark as in Example 4. Aftera reaction time of about 48 hours, the product is chromatographed onsilica with CH₂ Cl₂ /CCl₄ eluent to yield the title compound.

C. Cofacial-bis- cis-ethenyl meso-bridged!porphyrin CEBP! (Formula (5))and Polymeric-bis- cis-ethenyl meso-bridged! porphyrin PABP! (Formula(6))

5,15-Dibromo-10,20-diphenylporphyrinato zinc (0.2 mmol) and Pd(PPh₃)₄(0.02 mmole) are dissolved in 25 ml dry, degassed THF. A solution ofcis-bis(tri-n-butyltin)ethene (0.2 mmol) in 5 ml THF is added and thesolution heated at reflux for 2 days. The reaction is quenched withwater, extracted with methylene chloride, dried over calcium chloride,and the solvents are evaporated. The crude solid is chromatographed onsilica using methylene chloride/hexane eluant to isolate theCofacial-bis- cis-ethenyl meso-bridged!zinc porphyrin complex of formula(5) and Polymeric-bis- cis-ethenyl meso-bridged! porphyrin species offormula (6), wherein R_(A1) and R_(A3) are phenyl and M is Zn. ##STR5##

D. Fluorinated Cofacial-bis- cis-ethenyl mesobridged! porphyrin FCEBP!and Fluorinated Polymeric-bis- cis-ethenyl meso-bridged! porphyrinFPEBP!

5,15-Dibromo-10,20-bis(pentafluorophenyl)porphyrinato zinc (0.2 mmol)and Pd(PPh₃)₄ (0.02 mmol) are dissolved in 25 ml dry THF. A solution ofcis-bis(tri-n-butyltin)-1,2-difluoroethene (0.02 mmol) in 5 ml THF isadded and the solution heated at reflux for 2 days. The reaction isquenched with water, extracted with methylene chloride, dried overcalcium chloride, and the solvents evaporated. The crude solid ischromatographed on silica using methylene chloride/hexanes eluent toisolate the Cofacial-bis- cis-ethenyl meso-bridged! zinc porphyrincomplex as well as the Polymeric-bis- cis-ethenyl meso-bridged!porphyrin species. The cofacial and polymeric species are dissolvedseparately in chloroform. The cofacial porphyrin complex dissolved inchloroform and reacted with a large excess of N-bromosuccinimide as inExample 2 to perbrominate positions R_(B1) -R_(B8) on both porphyrins.The resulting material filtered through a fine fritted disk and washedwith water, methanol, and acetone, dried in vacuo, and thenrecrystallized from THF/heptane to yield the title compound. Theisolated material is reacted with Pd(dppf) and a large excess of CuCF₃in the dark in a manner as in Example 4. After a reaction time of about48 hours, the product is chromatographed on silica with CH₂ Cl₂ /CCl₄eluent to yield a perfluorinated CEPB analogous to formula (5).Perfluorinated PEBP is synthesized in a similar manner, yielding aspecies analogous to formula (6) where highly fluorinated porphyrins arelinked via fluorovinyl units.

E. Cofacial-bis- 1,8-anthracenyl-meso-bridged! porphyrin CBAP! (Formula(7)) and Polymeric-bis- 1,8-anthracenyl-meso-bridged! PBAP! porphyrin(Formula (8))

5,15-(Dibromoporphyrinato)zinc (0.2 mmol) and Pd(PPh₃)₄ (0.02 mmol) aredissolved in 25 ml dry, degassed THF. A solution of1,8-anthracenyl-bis-(tributyl tin) (0.2 mmol) in 5 ml THF is added andthe solution heated at reflux for 2 days. The reaction is quenched withwater, extracted with methylene chloride, dried over calcium chloride,and the solvents are evaporated. The crude solid is chromatographed onsilica using methylene chloride/hexane eluant to isolate theCofacial-bis- 1,8-anthracenyl-meso-bridged! zinc porphyrin complex offormula (7) and the Polymeric-bis- 1,8-anthracenyl-meso-bridged! zincporphyrin species of formula (8), where R_(A1) and R_(A3) are phenyl andM is Zn. ##STR6##

EXAMPLE 7 ACETYLENIC PORPHYRIN POLYMERS

A. Poly(5,15-bis(ethynyl)-10,20-diphenyl-porphyrinato zinc)

5,15-Bis(ethynyl)-10,20-diphenylporphyrinato zinc (0.2 mmol) in pyridine(20 ml) is slowly added to a solution of cupric acetate (0.4 mmol) in 20ml 1:1 pyridine/methanol generally according to the procedure ofEglinton, et al., The Coupling of Acetylenic Compounds, p. 311 inAdvances in Organic Chemistry, Raphael, et al., eds., 1963, IntersciencePublishers.

B. Poly(5,15-bis(ethynylphenyl)-10,20-diphenylporphyrinato zinc)

5,15-Diethynyl-10,20-diphenylporphinato zinc (0.2 mmol) and1,4-dibromobenzene are combined in a mixture of 30 ml toluene and 10 mldiisopropylamine. Cul (0.4 mmol) and Pd(Ph₃)₄ (0.02 mmol) are added andthe mixture is heated at 65° C. for 3 days. The crude solid is washedwith methanol and acetone and dried in vacuo.

Alternatively, the polymer is prepared from 1,4-diethynylbenzene and5,15-dibromo-10,20-diphenylporphinato zinc via the identical procedure.

EXAMPLE 8 DOPED PORPHYRIN POLYMERS

5,15-Bis(ethynyl)-10,20-diphenylporphyrinato zinc is polymerizedaccording to the general procedure provided by Skotheim, ed., Handbookof Conducting Polymers, Volume 1, pp. 405-437, Marcel Dekker, 1986 usinga catalytic amount of MoCl₅, Mo (CO)₆, WCl₆, or W(CO)₆. The resultantpolymer is then doped with an oxidant such as iodine or SbF₅.

EXAMPLE 9 METALATION OF BROMINATED PORPHYRINS

Finely divided zinc metal was prepared generally according to the methodof Rieke (J. Org. Chem. 1984, 49, 5280 and J. Org. Chem. 1988, 53, 4482)from sodium naphthalide and zinc chloride (0.18 mmol each) in THF. Asolution of 5-bromo-10,20-diphenylporphinato!zinc (100 mg, 0.17 mmol)dissolved in 40 mL THF was added by syringe to the zinc metalsuspension, and the mixture was stirred at room temperature overnight;during this time all of the zinc metal dissolved. The ring-metalatedporphyrin is suitable for palladium-catalyzed coupling with a variety ofaryl and vinyl halides.

EXAMPLE 10 PALLADIUM-CATALYZED CROSS-COUPLING WITH RING-METALATEDPORPHYRINS

5- (10,20-Diphenylporphinato)zinc!zincbromide (0.2 mmol) is prepared in15 mL of THF as in Example 9 above and is placed in a dry 100 mL Schlenktube. A solution of 2-iodothiophene (0.4 mmol) in 5 mL of THF is addedvia syringe. Pd(dppf) (3 mg) is prepared by stirring a suspension ofPd(dppf)Cl₂ in THF over Mg turnings for 20 min. and is transferred intothe reaction mixture by canula. The solution is stirred overnight,quenched with aqueous ammonium chloride, extracted with CH₂ Cl₂, anddried over CaCl₂. The solvent is evaporated to dryness andchromatography is carried out with 1:1 CH₂ Cl₂ as eluant. The product,5-(2-thiophenyl)-10,20-diphenylporphinato!zinc, elutes in one band andis isolated in 90% yield.

EXAMPLE 11 POLYMERIZATION WITH RING-METALATED PORPHYRIN DERIVATIVES

5,15-Bis(zinc bromide)-10,20-diphenylporphinato!zinc (0.2 mmol) isprepared in 15 mL of THF as in Example 9 and is placed in a dry 100 mLSchlenk tube. A solution of 5,15-dibromo-10,20-diphenylporphinato!zinc(0.2 mmol) in 15 mL of THF is added by syringe. Pd(dppf) (3 mg) isprepared by stirring a suspension of Pd(dppf)Cl₂ in THF over Mg turningsfor 20 min. and is transferred into the reaction mixture by canula. Themixture is heated at 60° C. for 3 days, cooled to room temperature andfiltered through a fine-fritted glass disk. The filtered polymer iswashed with hexane followed by methanol and dried in vacuo.

EXAMPLE 12 CARBONYLATION OF 5-BROMO-10,20-DIPHENYLPORPHINATO!ZINC

5- (10,20-Diphenylporphinato)zinc!magnesium bromide (0.2 mmol) isprepared in 15 mL of THF as in Example 9 and is placed in a dry 100 mLSchlenk tube. The vessel is cooled to 0° C. and dry CO₂ gas is bubbledthrough the solution. The solution is stirred for 1 h at roomtemperature, quenched with 0.1M HCl, extracted with CH₂ Cl₂, and driedover CaCl₂. The solvent is evaporated to dryness and chromatography iscarried out with THF:CH₂ Cl₂ as eluant. Upon evaporation of the solvent5-carboxy-10,20-diphenylporphinato!zinc is isolated in 85% yield.

EXAMPLE 13 COUPLING ON UNMETALATED PORPHYRIN DERIVATIVES

A. Using Organozinc Chloride Reagents

Trimethylsilylacetylene (3 mmol) was deprotonated with n-butyl lithium(3 mmol) at -78° C. in THF and warmed slowly to room temperature. ExcessZnCl₂ (650 mg) in 5 mL of THF was transferred into the solution viacanula. Pd(dppf) (3 mg) was prepared by stirring a suspension ofPd(dppf)Cl₂ in THF over Mg turnings for 20 min. and transferred into thesolution by canula. The entire reaction mixture was transferred to a dry100 mL Schlenk tube containing 340 mg of5,15-dibromo-10,20-diphenylporphyrin. The solution was heated to 40° C.and left sealed overnight. TLC of the reaction mixture after 18 h showsa mixture of fluorescent products. The mixture was quenched with aqueousammonium chloride, extracted with CH₂ Cl₂, and dried over CaCl₂. Thesolvent was evaporated to dryness and chromatography was carried outwith 1:1 CH₂ Cl₂ :hexane as eluant. The majority of the material wascollected in two bands which proved to be5-(2-trimethylsilylethynyl)-10,20-diphenylporphinato!zinc and5,15-bis(2-trimethylsilylethynyl)-10,20-diphenylporphinato!zinc. The twoproducts were isolated in 83% overall yield.

B. Using Organotrialkyltin Reagents

5,15-Dibromo-10,20-diphenylporphyrin is placed in a dry 100 mL Schlenktube and dissolved in 30 mL of THF. A solution of vinyltributyltin (3mmol) in 5 mL THF is added to the reaction mixture. Pd(dppf) (3 mg) isprepared by stirring a suspension of Pd(dppf)Cl₂ in THF over Mg turningsfor 20 min. and is transferred into the reaction mixture by canula. Thesolution is stirred overnight, quenched with aqueous ammonium chloride,extracted with CH₂ Cl₂, and dried over CaCl₂. The solvent is evaporatedto dryness and chromatography is carried out with 1:1 CH₂ Cl₂ :hexane aseluant. The product, 5,15-diphenyl-10,20-divinylprophyrin, elutes in oneband and is isolated in 90% yield.

EXAMPLE 14 COUPLING ON DILITHIALATED PORPHYRIN DERIVATIVES

A solution of N,N"-dilithio-5,15-dibromo-10,20-diphenylporphyrin (0.2mmol) in 15 mL of THF is prepared generally according to the method ofArnold, J. Chem. Soc. Commun. 1990, 976. A solution of vinyltributyltin(2 mmol) in 5 mL THF is added to the reaction mixture. Pd(dppf)(3 mg) isprepared by stirring a suspension of Pd(dppf)Cl₂ in THF over Mg turningsfor 20 min. and is transferred into the reaction mixture by canula. Thesolution is stirred overnight, and quenched with a solution of anhydrousNiCl₂ in THF. Aqueous ammonium chloride is added, the solution isextracted with CH₂ Cl₂, and dried over CaCl₁. The solvent is evaporatedto dryness and chromatography is carried out with 1:1 CH₂ Cl₂ :hexane aseluant. The product, 5,15-diphenyl-10,20-divinylporphinato!nickel,elutes in one band and is isolated in 90% yield.

Those skilled in the art will appreciate that numerous changes andmodifications may be made to the preferred embodiments of the inventionand that such changes and modifications may be made without departingfrom the spirit of the invention. For example, it is believed that themethods of the present invention can be practiced usingporphyrin-related compounds such as chlorins, phorbins,bacteriochlorins, porphyrinogens, sapphyrins, texaphrins, andpthalocyanines in place of porphyrins. It is therefore intended that theappended claims cover all such equivalent variations as fall within thetrue spirit and scope of the invention.

What is claimed is:
 1. A process for preparing a substituting porphyrin,comprising the steps of:providing a porphyrin compound having formula(1) or (2): ##STR7## wherein M is a chelated metal atom and at least oneof R_(A1) -R_(A4) or R_(B1) -R_(B8) is a first halogen; contacting saidporphyrin compound with a complex having formula Y(L)₂ wherein Y is afirst metal and L is a ligand, said contacting being performed underconditions effective to produce a first reaction product; contactingsaid first reaction product with an organometallic compound havingformula T(R_(L))_(z) (R_(O)), T(R_(L))_(z) (R_(O))_(t) (X_(B))_(w),T(R_(O)) (X_(B)) or T(R_(O))_(t) where:T is a second metal; X_(B) is asecond halogen or an alkoxy group; R_(L) is cyclopentadienyl or arylhaving about 6 to about 20 carbon atoms; R_(O) is alkyl, alkenyl oralkynyl having 1 to about 10 carbon atoms, aryl having about 6 to about20 carbon atoms; and z and w are greater than or equal to 0 and t is atleast 1;said contacting being performed under conditions effective toproduce a second reaction product comprising a substituted porphyrinhaving formula (1) or (2) wherein at least one of at least one of R_(A1)-R_(A4) or R_(B1) -R_(B8) is R_(O).
 2. The process of claim 1 whereinsaid first halogen is Cl or Br.
 3. The process of claim 1 wherein Y isPd, Ni, Pt, Ru, or Cu.
 4. The process of claim 1 wherein Y is Pd or Niand L is an alkylphosphine, arylphosphine, or a nitrogen-containingheterocycle.
 5. The process of claim 1 wherein said first reactionproduct includes a compound having formula P_(N) -Y(L)₂ X_(A) whereinP_(N) is said porphyrin compound and X_(A) is said first halogen.
 6. Theprocess of claim 1 wherein T is Li, Na, K, Rb, Cs, Hg, Sn, Al, B, Si,Zn, Zr, Cd, Cu, or Mg.
 7. The process of claim 1 wherein said secondreaction product includes a compound having formula P_(N) -Y(L)₂ R_(O)wherein P_(N) is said porphyrin compound.
 8. The process of claim 1wherein R_(O) is C(R_(C))═C(R_(D)) (R_(E)), C.tbd.C(R_(D)), haloalkylhaving from 1 to about 20 carbon atoms, or haloaryl or haloheteroarylhaving about 6 to about 20 carbon atoms, and R_(C), R_(D), and R_(E)are, independently, H, F, Cl, Br, I, alkyl or heteroalkyl having from 1to about 20 carbon atoms, aryl or heteroaryl having about 6 to about 20carbon atoms, alkenyl or heteroalkenyl having from 1 to about 20 carbonatoms, alkynyl or heteroalkynyl having from 1 to about 20 carbon atoms,trialkylsilyl, porphyrinato or a chemical functional group comprising apeptide, nucleoside or saccharide.
 9. A process for derivatizing aporphyrin compound, comprising the steps of:providing a porphyrincompound having formula (2): ##STR8## wherein at least one of R_(A1)-R_(A4) or R_(B1) -R_(B8) is a first halogen;and M is chelated metalatom; and contacting said porphyrin compound with a complex havingformula Y(L)₂ where Y is a metal and L is a ligand, said contactingbeing performed under conditions effective to produce a first reactionproduct that includes a compound having formula P_(N) -Y(L)₂ X_(A)wherein P_(N) is said porphyrin compound and X_(A) is said firsthalogen.
 10. The product of the process of claim
 9. 11. The process ofclaim 9 further comprising contacting said first reaction product withan organometallic compound having formula T(R_(L))_(z) (R_(O)),T(R_(L))_(z) (R_(O))_(t) (X_(B))_(w), T(R_(O)) (X_(B)) or T(R_(O))_(t)where:T is a Li, Zn, Cd, Cu, Sn, Mg or Zr; X_(B) is a second halogen oran alkoxy group; R_(L) is cyclopentadienyl or aryl having about 6 toabout 20 carbon atoms; R_(O) is C(R_(C))═C(R_(D)) (R_(E)),C.tbd.C(R_(D)), haloalkyl having from 1 to about 20 carbon atoms, orhaloaryl or haloheteroaryl having about 6 to about 20 carbon atoms, andR_(C), R_(D), and R_(E) are, independently, H, F, Cl, Br, I, alkyl orheteroalkyl having from 1 to about 20 carbon atoms, aryl or heteroarylhaving about 6 to about 20 carbon atoms, alkenyl or heteroalkenyl havingfrom 1 to about 20 carbon atoms, alkynyl or heteroalkynyl having from 1to about 20 carbon atoms, trialkylsilyl, porphyrinato or a chemicalfunctional group comprising a peptide, nucleoside or saccharide; and zand w are greater than or equal to 0 and t is at least 1;said contactingbeing performed under conditions effective to produce a second reactionproduct that includes a compound having formula P_(N) --Y(L)₂ R_(O). 12.The product of the process of claim 9.